Method of determining proportions



G. HERZOG METHOD OF DETERMINING PROPORTIONS Oct. 7, 1952 IN COMPOSITIONS OF SUBSTANCES Filed June 20, 1950 FFA C 770 /V/ TOE.

MM W E Patented Oct. 7, 1952 METHOD F DETERMINING 4PRDP()R/'LIVOINTS IVN COMPOSITIONS 0F SUBSTANCES Gerhard Herzog, Houston, 'Eex.,assig`norfto The Texas Company, New York, .Ni-3C., a Acorporation of Delaware Application Juneau, 195o, serial No; 169,257

1 This invention relates to a methodoimeasuring or controlling the proportions or ratio of two substances in a composition of those substances and it is the principal object of the invention to provide a method of this kindby means of which accurate determinations can be madeY of the proportions of two substances in a composition regardless ofthe formof the composition, i. e., regardless of whether it is a mixture, a solution, emulsion, suspension or a. chemical combination and without the necessity ofany deformation of the composition, if a solid, and without access to the interior of the vessel or pipe containing the composition, if'in the formv of a fluid.

flhis is a division of my copending application Serial No. 574,135, led'J'an'uary 23, 1945.r

`Many dim'culties are encountered in connectionwth the determination or measurement of the proportions of two substances in. a composition where access is not readily obtainable to the interiorof the vessel or pipe holding the composition. Again, wherethe composition is in the form oi,` say, a'sample of a solid it is very difficult to determine the proportions of the constituents without removing a portion of the sample. or otherwise disguring or deforming the sample in order to make the analysis. As an example, let us assume that a composition is formed of two substances either in a homogenous or` a nonhomogenous mixturey and in the form of, say,

a' block or a brick. Without removing a portion of the block for chemical. analysis, it would obviously be difficult to determine the proportions of` the two substances. As another example, suppose that a uid is owing through a pipe and thatthe uid is formed of twosubstances the ratio of which it is desired to ascertain. Without removing a sample ofv the flowing fluid for analysis by weighing or by chemical means, it would obviously be dicult to determine the exact ratio of the two substances forming the iiuid. It would be still more difficult to make a continuous record showing substantially instantaneously variations in the. ratio of the twoL fluids without continuously removing or by-pa-ssing a small amount of the iiui'd` to be used for analysis.

In accordance with the present invention'a method has been devised through` the use of which the desired. results mentioned above, i. e., measurement orV control. of the. proportions'of substances in a composition, canbe obtained, and this` regaro'llessn of thetform of the'. composition, i'.. e., whetheri'itlis atsolid oraffluid mixture, a solution,` emulsion-l suspensionl or a chemical combinatiom.` Through the use of the invention it `is also possible -to determinevariations in temperature which may` occur in the composition, such as" a 'iluid 11o-'wing through a pipe, 'without removing samples and without any access to the'interior'of the pipe for the insertion of `thermo'couple elements,` or thevflike.

In-carrying out the' invention, a beam of penetrative radiation `is'transmitted through the composition, the proportions of which it is desired to ascertain and a measurement is made of the intensity of' the radiation after it has traversed the com-position. The length of the path 'of the beam throughthe composition mayv be selected sothat a p'redeterminedvaccuracyV can be obtained.- Thu's, the beam may pass diagonally through 'a 'pipe' carrying a' fluid composition or itmay-pass through a selected portion of a vessel inifwhichrthe composition is being treated. By proper calibration ofthe measuring instrument, the intensity' reading can be made to ind'icate' directly the ratio 'of the' two substances in the composition being examined. For calibration purposes afmeasurem'ent as described above can" be made where the beam oi radiation is transmitted through each ofthe substances separately providing that the'length of the path of' the beam' through thel substances is the saine as in' thev case where` the beam is' transmitted through the mixture or composition. If desired, instead-of measuringthe intensity of the radiation passing through each of the substances taken alone, measurements can'be'made through known mixtures, i. e., compositions wherein the proportions ortlfn-rrat'io` ofA the twosubstances areknown',` anda calibration curve then prepared from'which theratio of the substances in an un'- known composition can subsequently be read directly.

As an example of an application of the inventiona description will be given of the use of they method-as applied, in determining the ratio of acid catalyst toi hydrocarbons in an alkylation process wherein isoparafnichydrocarbons are alkylated to produce hydrocarbons suitable for an aviation type motor fuel.

' For a better understanding of the invention reference may be had to the accompanying drawing in which:l

Fig. 1 is a somewhat diagrammatic'illu'stration through a vessel containing a composition of two substances theI ratio of which it is'desired to ascertain,

lig. 2 is a vertical elevation showing apparatus used in an alkylation process,

Fig. 3 is a diagram to which reference willbe made in explaining the principles of the inven tion,

Fig. 4 is an enlarged view through a section of pipe showing a somewhat different arrangement of the radiation source and detector, while Fig. 5 is a sectional plan view through a vessel showingan arrangement of apparatus for controlling the proportions of substances lof a composition within the vessel.

In Figure 1 of the drawing a vessel I8 is shown as containing a quantity of a composition I2 which may be a mixture of two substances or an emulsion, solution or chemical composition of the two substances. A housing or block I4 of a material such as lead capable of absorbing gamma radiation contains at its inner surface a small amount of a radioactive substance IS, such as radium and a beam of the penetrativel radiation,

indicated diagrammatically by the dotted line22,

is transmitted through the walls of the vessel I0 and through the composition I2. YAt another side of the vessel ID is a housing 24 containing a suitable detector 26 of penetrative radiation-which may comprise a Geiger-Mller counter, a proportional counter or an ionization chamber. The detector 2S is connected to a suitable amplifier 28, the output of which is in turn led to a measuring instrument such as the meter 3U. If desired, a suitable preamplifier may be disposed within the housing 24.

With reference to Figure 3 let us assume that the side walls of the vessel IU of Figure 1 are denoted by the vertical lines I0' and that these walls have no appreciable thickness; that the intensity of the incoming radiation beam is indicated at Io and that the intensity of the radiation emerging from the vessel is indicated by I. Also let us assume that there are two substances a and b in the vessel and the cross-hatched portions indicate the relative proportions of these two substances in the path of the beam of transmitted radiation. For purposes of illustration only, the amount of the substance a is indicated by the block or section marked a as though this substance were all in one place. likewise that the substance b is positioned in one placein alignment with the radiation source and the substance a. Then the distance .1: will designate the proportion of the substance a in the mixture or composition and Z minus designates the portion of I the substance 12, Z, of course, indicating the length-of the path of the beam through the composition.

First let us assume that there is only one substance in the vessel I8 and that the beam of radiation therefore passes through nothing other than this substance ,a and the walls of the vessel. Then,

Ia:I)e"kal (l) where Ia is the intensity of the radiation which has passed through the substance a, and ka is the absorption coefficient for the substance a.

Assuming then that the substance b is the only substance in the path of the beam of radiation,

IbzIn-kbl (2) where kb is the absorption coeicient for the substance b.

Let us assume now that both substances are in the vessel as shown in Figure 3 and that I' is the intensity of the radiation afterl it has passed through the substance a and before it reaches the substance 19, f then From Equations 1, 2 and 5 one can solve for the three unknowns ka, kb and If l is assumed to be one then a: will be the percentage of the substance a in the composition ab. In this discussion we have assumed that the walls have no thickness. In an actual case where the composition is in a container, the equations would obviously include a factor to represent the absorbing effect of the walls.

It is to be understood that the substances a and b within the path of the radiation beam can be mixed in any manner or they can comprise a solution, an emulsion or dispersion, or a chemical combination ofthe two substances since the absorption of the radiation in the composition depends only upon the atomic structure.` In other words, the absorption of gamma rays depends on the number of atoms per unit volume and it remains unchanged as long as the number of atoms remains the same, regardless of the nature of the composition, i. e., whether it is in the form of a mixture, solution, etc.

It will be clear from the above that once the measurements are obtained for each substance separately, it will thereafter be necessary merely to take a single reading on any mixture or solution of these substances and from that reading the proportion or ratio of the substances can be quickly determined. If desired, a curve can be prepared either for the two substances separately or for known ratios of the two substances, and then the ratio o f the unknown composition read directly from the curve. While the container I0 has been described as a vessel, it is contemplated that it may be a pipe or conduit through which the composition I2 is owing. The pipe should be full so that the length of the path of the radiation beam through the composition will not vary.

In Figure 2 the invention is illustrated as applied to the determination of the ratio of the acid catalyst to the hydrocarbons in the emulsion iiowing from a contactor of the Stratco type in an alkylation system. The contactor is represented at 32 into which the isoparainic hydrocarbons isobutane and butylene enter through the pipe 34. The fresh acid-catalyst enters the contactor through the pipes 38 and 38 and a motor 40 serves to drive an agitator, not shown, so as to emulsify the acid and hydrocarbons. The emulsion is drawn from the upper portion of the contactor 32 through the pipe 42 and is passed to a separator 44. Part of the acid settling in the separator may be recycled by means of the pump 46 through the pipe 38 into the contactor. The pipe 42 is illustrated as having a short vertical section 48 and on the opposite sides of this section are placed the housing I4 containing the source of radiation and the housing 24 containing the radiation detector. The output of the detector passes to the amplifier 28 and then to the meter 30 as has been described hereinbefore. By placing the source and the detector at opposite sides of a vertical pipe one is assured that the pipe will remain full of the emulsion. Assuming that intensity mea-surements have been made of the acid alone and of the hydrocarbons alone when occupying the pipe section 48, or that the instrument 30 has been calibrated in any other suitable manner it is then merely necessary to observe or record the :reading o'i theimeter 30 f to detcrminesthefproaportions L or the :ratio: 'of ithexac'd andthe hydro.,- carbonewhen'the emulsion is'ipassing thrnugh :the pipese'ction 43.'` l

"The .greater `the dengthzof thevpath fof` the,I radiation through fthewcomposition, the more accu.- rate will Ibe-zthe measurements. Thus, if it is fdesiredto measure, density variations of vthe ondersnf; sayfpluszorlminus ;'50`B.in the emul- .housing 24; can z beV raised or 'lowered on` the Apipe 4,8motliat .'thetpath io'f thebeam willbe suiliciently jlongto. providesthis accuracy.. In .Figure 4 is an 4enlargedf section of; a pipe which may, :for instance, be the pipe 48 of Figure 2..,with thehousing L4. containingthe source positioned against the outer` surface of the pipe and the housing 24 containing a detector..f26positioned. adjacent the .ohpositesideof the pipo but in alower position with respect tothe housing I4. vhefpath of the beam 22 is therefore increasedandgreater accuracy will beatt'ained. The sourcemust, of course, have= suiiicient strength to` 'transmit radiation through the :desire-d path22 ,toactuate the' de- Figure 5 is a sectional plan-view showing a modication in which a housing l4a containing a source of radiation is mounted on the exterior surface 4of a vessel 32a, which may be, for instance, the contactor 32 of Figure 2. Also disposed adjacent the exterior of the vessel across, but not necessarily exactly opposite the housing I4a, is a housing 24a containing a radiation detector 26a. The housing 24 is positioned with respect to the housing Ida so that the radiation beam 22a within the emulsion will be long enough to provide measurements of the desired accuracy. In this manner the acid-hydrocarbon ratio of the emulsion 32a can be measured while the emulsion is still being circulated within the vessel.

Although the invention has been described as a method of measuring or determining ratios of substances in a composition, it is contemplated thatthese determinations can be used in connection with control in manufacturing processes. As shown in Figure 5, the vessel 32a is provi-ded with two intake pipes or conduits 50 and 52, one for each of the substances to be treated within the vessel. The conduit 52 is provided with a valve 54 actuable by suitable means such as a solenoid illustrated diagrammatically at 56. The output of the detector 26a is connectedto an amplifier 28a the output of which in turn is led to a relay 58. The relay is connected to the solenoid 56 and is adapted in any well known manner to connect a source of electric current 60 to the solenoid when the relay is actuated by a predetermined increase or decrease in the output of the amplifier 26a. Thus, assuming for example that isobutane-butylene enters the vessel 32a through the pipe 50 and that the acid catalyst enters through the pipe 52, the apparatus shown in Figure 5 can be easily adjusted to maintain a desired ratio between these substances in the emulsion within the vessel 32a. In case the ratio should change more than an allowable amount, Jche response of the detector 26a. will change and .the amplier output will cause the relay 58 to operate to actuate the solenoid 56 to open or close the valve 54. as the case may be, to control the amount of acid owing into the vessel 32a.

The method isapplicable in many other processes such as in continuous grease manufacture to assure uniformity of batches, in determining the extent of polymerization in rubber manufacture, the extent of cracking and the extent of in temperatureinthe composition, the invention is also applicable inthe determining-or measuring of` temperature. Thus, with referenceagain tofFigure 2, if the'meterr is calibratedin temperature and' the temperature of the .emulsion passing through the pipe section 48 changes, the density of` the emulsion will change accordingly and the-meter-'Sdwill show a `different reading, indicating the new temperature. Thus without the use `of thermometers, thermocouples and-the like, and without ythe necessity of access to-the interior o'flthe -pipe section 48, indications or a record may be had of these temperature variations.- There is usually a lag in the action of most temperature sensitive devices such as thermocouples and the like but With the present method the meter 3e will respond substantially instantaneously to variations in density of the composition within the pipe 48, and thus to Variations in temperature.

While the source I6 has been described as radium and the radiation beam as comprising gamma rays, it is Ito be understood that other types of radiation can be used. For instance, neutrons emitted from a mixture of radium and berylium could be utilized, the detector 26 in such a case comprising preferably an ionization chamber or a proportional counter. Likewise, in certain instances an articially radioactive source may be advantageous. Where penetrative radiation is referred to in the claims, it is contemplated that any oi these radiations or others, such as for example, X-rays, alpha rays, electrons and protons can be used.

It is to be understood that in the claims which follow, although reference may be made to a specic form of composition such as a mixture, it is intended that all other forms of composition are to be included within the meaning of this term, such as solutions, emulsions, suspensions, dispersions, chemical combinations and the like.

Obviously many other modications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof, but only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. The method of determining the proportions of two substances in a mixture which comprises transmitting a beam of neutrons through said mixture over a predetermined path, transmitting said beam through mixtures of said substances wherein Ithe ,proportions of the substances are known while maintaining the length of the path of two substances. in a composition flowing through a pipe which comprises transmitting substantially laterally through said pipe a beam of neutrons when the pipe is conducting a ccmposition of said substances and when the pipe contains each substance separately, observing the intensities of the beam after it has traversed the pipe, and from the measurements so obtained calculating said proportions.

3. The method of determining the ratio of two substances in a composition which comprises transmitting a beam of neutrons through said composition and through other compositions of the same substances wherein the ratio of the substances is known, while maintaining constant the lengths of the paths of said beam through the known and unknown compositions, and measuring the intensities of the radiation after passing through said compositions, and from said measurements calculating the proportions of the substances in the first mentioned composition.

4. rl'he method of determining the proportions of two substances in a mixture in an opaque container which comprises transmitting through said container and said substances a beam of neutrons, repeating this operation when the container holds mixtures of said substances in known proportions, observing the intensities of the beam during each transmission, and from the measurements so obtained, calculating said proportions.

5. The method of determining the proportions of two substances in a mixture in an opaque container which comprises transmitting a beam of neutrons through at least a portion of the mix- Iture in said container, repeating this operation when the container holds mixtures of said substances in known proportions while maintaining the length of the path of said beam the same as for said iirst transmission, observing the intensi- Ities of the beam during each transmission, and from the measurements so obtained calculating said proportions.

GERHARD HERZOG.

REFERENCES CITED The following references are of record in the iile of this patent:

UNITED STATES PATENTS Number Name Date Re. 22,531 Hare Aug. 22, 1944 2,487,797 Friedman et al. Nov. 15, 1949 2,534,352 Herzog Dec. 19, 1950 

1. THE METHOD OF DETERMINING THE PROPORTIONS OF TWO SUBSTANCES IN A MIXTURE WHICH COMPRISES TRANSMITTING A BEAM OF NEUTRONS THROUGH SAID MIXTURE OVER A PREDETERMINED PATH, TRANSMITTING SAID BEAM THROUGH MIXTURES OF SAID SUBSTANCES WHEREIN THE PROPORTIONS OF THE SUBSTANCES ARE KNOWN WHILE MAINTAINING THE LENGTH OF THE PATH THE SAME AS FOR SAID FIRST TRANSMISSION, MEASURING THE INTENSITIES OF SAID BEAM AFTER BEING TRANSMITTED THROUGH SAID UNKNOWN MIXTURE AND SAID KNOWN MIXTURES, AND FROM A COMPARISON OF THE MEASUREMENTS SO OBTAINED CALCULATING THE PROPORTIONS OF THE SUBSTANCES IN THE UNKNOWN MIXTURE. 